全文获取类型
收费全文 | 259篇 |
免费 | 38篇 |
国内免费 | 8篇 |
专业分类
化学 | 280篇 |
晶体学 | 2篇 |
力学 | 2篇 |
物理学 | 21篇 |
出版年
2024年 | 1篇 |
2023年 | 3篇 |
2022年 | 14篇 |
2021年 | 11篇 |
2020年 | 21篇 |
2019年 | 13篇 |
2018年 | 10篇 |
2017年 | 15篇 |
2016年 | 22篇 |
2015年 | 12篇 |
2014年 | 11篇 |
2013年 | 30篇 |
2012年 | 12篇 |
2011年 | 14篇 |
2010年 | 8篇 |
2009年 | 7篇 |
2008年 | 17篇 |
2007年 | 11篇 |
2006年 | 12篇 |
2005年 | 4篇 |
2004年 | 7篇 |
2003年 | 11篇 |
2002年 | 5篇 |
2001年 | 5篇 |
2000年 | 3篇 |
1999年 | 2篇 |
1998年 | 2篇 |
1997年 | 3篇 |
1996年 | 2篇 |
1995年 | 1篇 |
1994年 | 5篇 |
1992年 | 4篇 |
1991年 | 2篇 |
1987年 | 1篇 |
1982年 | 1篇 |
1981年 | 1篇 |
1980年 | 1篇 |
1974年 | 1篇 |
排序方式: 共有305条查询结果,搜索用时 15 毫秒
1.
Weiyi Li Geng Leng Caiqin Li Yajing Lyu 《International journal of quantum chemistry》2020,120(8):e26150
The mechanisms of CO2 coupling with the propargylic alcohol using alkali carbonates M2CO3 (M = Li, Na, K, Cs) have been investigated by means of density functional theory calculations. The calculations reveal that the target product tetronic acid (TA) is yielded through two stages: (a) the formation of the α-alkylidene cyclic carbonate (αACC) intermediate via Cs2CO3-mediated carboxylative cyclization of the propargylic alcohol with CO2, and (b) the conversion of the αACC intermediate with Cs2CO3 to produce the cesium salt of the TA. Since the overall kinetic barriers for the two stages are comparable and affordable, the excellent chemoselectivity to the TA should be primarily originated from the high thermodynamic stability of the cesium salt of the TA. Moreover, relative to the TA, the possibility to yield the by-product acyclic carbonate can be excluded due to the both kinetics and thermodynamic inferiority. This result is different from the organic base-mediated reaction. Alternatively, our calculations predict that CsHCO3 together generated with the cesium salt of the TA might also be an available mediating reagent for the incorporation of CO2 with the propargylic alcohol. Compared to other alkali carbonates M2CO3 (M = Li, Na, K), the stronger basicity of Cs2CO3 and the lower ionic potential of cesium ion can raise the effective concentration of the αACC intermediate, and thus the conversion of the αACC intermediate into the cesium salt of the TA can be achieved with high yield. 相似文献
2.
Roser Cervellera Xavier Ramis Josep Maria Salla Ana Mantecn Angels Serra 《Journal of polymer science. Part A, Polymer chemistry》2006,44(9):2873-2882
N,N‐Dimethylaminopyridine (DMAP) was used as initiator to cure mixtures of diglycidylether of bisphenol A (DGEBA) and 1,3‐dioxan‐2‐one (TMC) or 5,5‐dimethyl‐1,3‐dioxan‐2‐one (DMTMC). The curing was studied by differential scanning calorimetry (DSC) and Fourier transform infrared in the attenuated‐total‐reflection mode (FTIR/ATR). FTIR/ATR was used to monitor the competitive reactive processes and to quantify the evolution of the groups involved in the curing. We observed the formation of five‐membered cyclic carbonates and anionic carbonate groups that remain unreacted at the chain ends. The formation of these groups was explained by the attack of the anionic propagation species on the methylene carbon of the carbonate group, which leads to an alkyl‐oxygen rupture. By performing the cure in the thermobalance we could evaluate the loss of CO2 produced in the samples containing carbonates. The kinetics were studied by DSC and analyzed with isoconversional procedures. The addition of carbonates slows down the curing rate. Thermogravimetric analysis (TGA) and dynamic mechanical thermal analysis (DMTA) experiments were used to evaluate the properties of the materials obtained. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2873–2882, 2006 相似文献
3.
聚(酪氨酸酯对苯二甲酰胺)碳酸酯药物控制释放材料的研究 总被引:2,自引:0,他引:2
报道了一类生物可降解聚(酪氨酸酯对苯二甲酰胺)碳酸酯的合成和结构表征,研究了聚合物的性质和体外降解性能,并以5 氟脲嘧啶和牛血清白蛋为模型,对它们作为药物控制释放材料的性能进行了初步评价. 相似文献
4.
Reaction of the vicinal diols of steroids1, 5, 7, 10, 13, and16 with TPP/DEAD yields both regio-and stereospecifically the oxosteroids2, 6, 8, 11, 14, and15 by displacement of an axial hydrogen and extrusion ofTPPO besides the cholest-4-en-6-ols9 and12 and the cyclic carbonate3. 16, 17-androstandiol16 gives only the cyclic carbonate17. The different structures of the carbohydrates withcis-diol arrangement19 and21 lead exclusively to cyclic carbonates20 and22 in moderate yields. Treatment of1 with TPP/DEAD/HN3 affords 3-azido-2-hydroxycholestane4 in addition to the above mentioned2. 相似文献
5.
The stoichiometric solubility constant of eitelite (NaMg
0.5
CO
3
+2H+ ⇄ Na++0.5Mg
2+
+CO
2
(g)+H
2
O, log*K
pso
I
=14.67±0.03 was determined at I=3 m (mol kg−1) (NaClO
4
) and 25°C. The stability of magnesium (hydrogen-)carbonato complexes in this ionic medium was explicitely taken into account.
Consequently, trace activity coefficients of free ionic species, calculated from the Pitzer model with ion-interaction parameters
from the literature, were sufficient for an evaluation of the thermodynamic solubility constants and Gibbs energies of formation
for eitelite (−1039.88±0.60), magnesite (−1033.60±0.40), hydromagnesite (−1174.30±0.50), nesquehonite (−1724.67±0.40), and
brucite (−835.90±0.80 kJ-mol
−1
). The increasing solubilities of nesquehonite and eitelite at higher sodium carbonate molalities were explained by invoking
a magnesium dicarbonato complex (Mg2++2CO
3
2−
⇄ Mg(CO3)
2
2−
, log βz = 3.90 ± 0.08). A set of ion-interaction parameters was obtained from solubility and dissociation constants for carbonic
acid in 1 to 3.5 m NaClO
4
media
which reproduce these constants to 0.02 units in log K. The following Pitzer parameters are consistent with the previously
studied formation of magnesium (hydrogen-)carbonato complexes in 3m NaClO
4
. The model and Gibbs functions of solid phases derived here reproduce original solubility data (−log [H+], [Mg
2+
]
tot
) measured in perchlorate medium within experimental uncertainty.
Presented at the XXII International Conference on Solution Chemistry, July 14–19, 1991, Linz, Austria. 相似文献
6.
7.
《Surface and interface analysis : SIA》2003,35(3):310-317
Carbonate is a somewhat enigmatic anion in static secondary ion mass spectrometry (SIMS) because abundant ions containing intact CO32? are not detected when analyzing alkaline‐earth carbonate minerals common to the geochemical environment. In contrast, carbonate can be observed as an adduct ion when it is bound with alkali cations. In this study, carbonate was detected as the adduct Na2CO3·Na+ in the spectra of sodium carbonate, bicarbonate, hydroxide, oxalate, formate and nitrite and to a lesser extent nitrate. The appearance of the adduct Na2CO3·Na+ on hydroxide, oxalate, formate and nitrite surfaces was interpreted in terms of these basic surfaces fixing CO2 from the ambient atmosphere. The low abundance of Na2CO3·Na+ in the static SIMS spectrum of sodium nitrate, compared with a significantly higher abundance in salts having stronger conjugate bases, suggested that the basicity of the conjugate anions correlated with aggressive CO2 fixation; however, the appearance of Na2CO3·Na+ could not be explained simply in terms of solution basicity constants. The oxide molecular ion Na2O+ and adducts NaOH·Na+ and Na2O·Na+ also constituted part of the carbonate spectral signature, and were observed in spectra from all the salts studied. In addition to the carbonate and oxide ions, a low‐abundance oxalate ion series was observed that had the general formula Na2?xHxC2O4·Na+, where 0 < x < 2. Oxalate adsorption from the laboratory atmosphere was demonstrated but the oxalate ion series also was likely to be formed from reductive coupling occurring during the static SIMS bombardment event. The remarkable spectral similarity observed when comparing the sodium salts indicated that their surfaces shared common chemical speciation and that the chemistry of the surfaces was very different from the bulk of the particle. Copyright © 2003 John Wiley & Sons, Ltd. 相似文献
8.
环状碳酸酯低聚物的合成及其开环聚合的研究 总被引:4,自引:0,他引:4
环状碳酸酯低聚物的合成及其开环聚合的研究陈雨萍魏玮李革(中国科学院化学研究所工程塑料国家重点实验室北京100080)关键词环状碳酸酯低聚物,聚碳酸酯,开环聚合环状单体的开环聚合在合成高聚物方面具有突出的优点,即在聚合过程中没有副产物、热效应低、聚合... 相似文献
9.
Aryane A. Marciniak Katie J. Lamb Leonardo P. Ozorio Claudio J.A. Mota Michael North 《Current Opinion in Green and Sustainable Chemistry》2020
- Download : Download high-res image (249KB)
- Download : Download full-size image
10.
Jan Samsonowicz-Grski Anna Brodzka Ryszard Ostaszewski Dominik Koszelewski 《Molecules (Basel, Switzerland)》2022,27(14)
Chiral amines and alcohols are synthons of numerous pharmaceutically-relevant compounds. The previously developed enzymatic kinetic resolution approaches utilize a chiral racemic molecule and achiral acyl donor (or acyl acceptor). Thus, only one enantiodivergent step of the catalytic cycle is engaged, which does not fully exploit the enzyme’s abilities. The first carbonate-mediated example of simultaneous double chemoselective kinetic resolution of chiral amines and alcohols is described. Herein, we established a biocatalytic approach towards four optically-pure compounds (>99% ee, Enantioselectivity: E > 200) via double enzymatic kinetic resolution, engaging chiral organic carbonates as acyl donors. High enantioselectivity was ensured by extraordinary chemoselectivity in lipase-catalyzed formation of unsymmetrical organic carbonates and engaged in a process applicable for the synthesis of enantiopure organic precursors of valuable compounds. This study focused not only on preparative synthesis, but additionally the catalytic mechanism was discussed and the clear impact of this rarely observed carbonate-derived acyl enzyme was shown. The presented protocol is characterized by atom efficiency, acyl donor sustainability, easy acyl group removal, mild reaction conditions, and biocatalyst recyclability, which significantly decreases the cost of the reported process. 相似文献